This invention relates to certain monocyclopentadienyl metal compounds, to certain catalyst systems comprising such monocyclopentadienyl metal compounds along with an activator, and to a process using such catalyst systems for production of polyolefins, particularly high molecular weight ethylene-xcex1-olefin copolymers having a high level of xcex1-olefin comonomer incorporation.
As is well known, various processes and catalysts exist for homopolymerization or copolymerization of olefins. For many applications it is of primary importance for a polyolefin to have a high weight average molecular weight while having a relatively narrow molecular weight distribution. A high weight average molecular weight, when accompanied by a narrow molecular weight distribution, provides a polyolefin or an ethylene-xcex1-olefin copolymer with high strength properties.
U.S. Pat. No. 5,264,504 discloses certain monocyclopentadienyl metal compounds having an amido radical with an aliphatic or alicyclic hydrocarbyl moiety attached thereto through a primary or secondary carbon atom. EPO 416,815 discloses certain monocyclopentadienyl metal compounds which are activated with an alumoxane co-catalyst. U.S. Pat. No. 5,064,802 discloses certain monocyclopentadienyl metal compounds which are activated with a non-coordinating compatible anion of a Bronsted acid salt.
The present invention is directed to certain monocyclopentadienyl compounds and to catalyst systems which include such monocyclopentadienyl metal compounds along with an activator component. The catalyst systems of the present invention are highly productive for polymerizing ethylene and olefins to produce high molecular weight copolymers having a high content of xcex1-olefin comonomer. More particularly, the present invention relates to certain monocyclopentadienyl metal compounds which include an amido moiety having an alicyclic hydrocarbyl moiety covalently bonded thereto through a tertiary carbon atom. A tertiary carbon atom is defined here as a carbon atom bonded to three other non-hydrogen atoms.
This invention relates to the discovery of certain monocyclopentadienyl metal compounds which, by reason of the presence therein of ligands of a particular nature, are particularly useful in catalyst systems to provide greatly improved performance characteristics. The monocyclopentadienyl metal compounds of the present invention are represented by the formula: 
wherein: M is Zr, Hf or Ti;
(C5H4xe2x88x92xRx) is a cyclopentadienyl ring which is substituted with from zero to four substituent groups R, xe2x80x9cxxe2x80x9d is 0, 1, 2, 3, or 4 denoting the degree of substitution, and each substituent group R is, independently, a radical selected from C1-C20 hydrocarbyl radicals, substituted C1-C20 hydrocarbyl radicals wherein one or more hydrogen atoms is replaced by a halogen radical, an amido radical, a phosphido radical, an alkoxy radical, an aryloxy radical or any other radical containing a Lewis acidic or basic functionality; C1-C20 hydrocarbyl-substituted metalloid radicals wherein the metalloid is selected from the Group IV A of the Periodic Table of Elements; halogen radicals; amido radicals; phosphido radicals; alkoxy radicals; alkylborido radicals; or any other radical containing Lewis acidic or basic functionality; or (C5H4xe2x88x92xRx) is a cyclopentadienyl ring in which at least two adjacent R-groups are joined together and along with the carbon atoms to which they are attached form a C4-C20 ring system;
Rxe2x80x2 is a radical selected from C4-C30, preferably C4-C20, alicyclic hydrocarbyl radicals wherein one or more hydrogen atoms may be replaced by radicals containing Lewis acidic or basic functionalities such as, for example, radicals selected from halogen, amido, phosphido, alkoxy, aryloxy and the like, with the proviso that Rxe2x80x2 is covalently bonded to the nitrogen atom through a tertiary carbon atom;
each Q is independently a radical selected from halide; hydride; substituted or unsubstituted C1-C20 hydrocarbyl; alkoxide; aryloxide; amide; or phospide; or both Q together may be an alkylidene or a cyclometallated hydrocarbyl or any other divalent anionic chelating ligand, with the proviso that where any Q is a hydrocarbyl radical, such Q is not a substituted or unsubstituted cyclopentadienyl radical;
T is a covalent bridging group containing a Group IV A or V A element such as, but not limited to, a dialkyl, dialicyclyl, alkylalicyclyl, arylalicyclyl, alkylaryl or diaryl silicon or germanium radical; alkyl and/or aryl phosphine or amine radical; or a substituted or unsubstituted hydrocarbyl radical such as methylene, ethylene and the like which may be substituted with substituents selected from alkyl, alicyclyl and aryl radicals or combinations thereof having from 1 to 20 carbon atoms and silyl atoms.
Such compounds can also include an Lw complexed thereto wherein L is a neutral Lewis base. Examples of such neutral Lewis bases include but are not limited to diethylether, tetraethylammonium chloride, tetrahydrofuran, dimethylaniline, aniline, trimethylphosphine, n-butylamine, and the like. The xe2x80x9cwxe2x80x9d is a number from 0 to 3. Optionally, L may be covalently bonded to one or both Q provided Q is not hydride or halide.
L can also be a second transition metal compound of the same type such that the two metal centers M and Mxe2x80x2 are bridged by Q and Qxe2x80x2, wherein Mxe2x80x2 has the same meaning as M, and Qxe2x80x2 has the same meaning as Q. Such dimeric compounds are represented by the formula: 
A preferred class of compounds of the present invention are represented by the formula: 
wherein:
M is selected from Ti, Hf and Zr;
(C5H4xe2x88x92xRx) is as defined above with respect to Formula I;
each of R1 and R2 are independently selected from C1-C20 hydrocarbyl radicals, and may optionally be joined together to form a cyclic ring structure;
T is Si or Ge;
each Q is independently selected from halide, hydride, substituted or unsubstituted C1-C20 hydrocarbyl radicals; alkoxide; amide; and phosphide radicals, with the proviso that Q is not a substituted or unsubstituted cyclopentadienyl radical;
Rxe2x80x2 is selected from C4-C20 alicyclic hydrocarbyl radicals with the proviso that Rxe2x80x2 is covalently bonded to the nitrogen atom through a tertiary carbon atom; and
Lw is optional and is as defined above.
A more preferred class of compounds of the present invention are those compounds represented by Formula IV: 
wherein:
M is selected from Ti, Zr and Hf;
T is selected from Si or Ge;
each of R1 and R2 is independently selected from C1-C20 alkyl, C6 C22 aryl, C3-C20 cycloalkyl radicals or combinations thereof and may optionally be joined together to form a cyclic ring structure;
each R3 is independently selected from hydrogen; C1-C20 alkyl; C3-C20 cycloalkyl; C6-C22 aryl; halogen; amido; phosphido; alkoxy; aryloxy; alkylborido; and the like radicals; or combinations thereof;
each Q is independently selected from hydrogen; halogen; C1-C20 alkyl; C6-C22 aryl; C3-C20 cycloalkyl; alkoxy; aryloxy; amido; and phosphido radicals or combinations thereof;
u is an integer of from 0 to 6, preferably 0 to 4, such as from 1 to 3;
x is 0-4;
each R4 is independently selected from hydrogen; halogen, C1-C10 alkyl; C3-C10 cycloalkyl; C6-C22 aryl; amido; alkoxy; aryloxy; or combinations thereof and the like radicals; or two R4 groups along with the carbon atom or atoms to which they are attached, form a saturated or partially saturated alicyclic group or form an aryl group; and
Lw is optional and is as defined above.
Preferred compounds within the scope of Formula IV are those wherein each R3 is independently selected from C1-C20 alkyl; C3-C20 cycloalkyl; C6-C22 aryl; or combinations thereof; and M is titanium. As utilized herein, the term xe2x80x9calkylxe2x80x9d, alone or in combination, means a straight-chain or branched-chain alkyl radical containing from 1 to about 20, preferably from 1 to about 10 carbon atoms. Examples of such radicals include methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, pentyl, iso-amyl, hexyl, octyl, decyl, dodecyl, and the like. Such alkyl and alicyclic radicals may carry one or more substitutes selected from alkoxy, halo, aryloxy, hydroxy, amino, phosphino, borido, nitro and the like. The term xe2x80x9calkoxyxe2x80x9d, alone or in combination means an alkyl oxy radical wherein the term xe2x80x9calkylxe2x80x9d is as defined above. Examples of suitable alkoxy radicals include methoxy, ethoxy, n-proxy, iso-propoxy, n-butoxy, sec-butoxy, tert-butoxy, pentoxy and the like. The term xe2x80x9calicyclicxe2x80x9d, alone or in combination, means a branched or unbranched cyclic alkyl radical as defined above which is saturated, or partially saturated. Examples of such alicyclic radicals include cyclopropyl, cyclobutyl, cyclohexyl, cyclododecyl, 2-methylcyclohexyl, norbornyl, adamantyl and the like. The term xe2x80x9carylxe2x80x9d, alone or in combination, means a mono, bi or poly aromatic radical. Examples of such radicals include phenyl, cycloheptatrienyl, naphthyl, anthracenyl, chrysenyl, azulenyl, biphenyl, p-terphenyl, 1-phenyl naphethyl and the like. Such aryl radicals may carry one or more substituents selected from alkyl, alkoxy, aryloxy, halogen, hydroxy, amino, phosphido, borido, nitro and the like. Examples of such substituted aryl radicals include p-tolyl, 4-methoxyphenyl, 4-t-butylphenyl and the like. The term xe2x80x9caryloxyxe2x80x9d, alone or in combination, means an aryl oxy radical wherein aryl is as defined above. Examples include phenoxy and the like. The term xe2x80x9chalogenxe2x80x9d or xe2x80x9chaloxe2x80x9d means fluoride, chloride, bromide or iodide radicals. The term xe2x80x9cring systemxe2x80x9d means a bi- or polycyclic system wherein one or more aromatic radicals is fused to one or more alicyclic and/or aryl radicals. Examples of such ring systems include fluorenyl, indenyl, tetrahydroindenyl, benzindenyl, and the like which systems may be substituted with one or more radicals such as alkyl radicals.
A tertiary (3xc2x0) carbon atom means a carbon atom which is bonded to three other non-hydrogen atoms. An alicyclic hydrocarbyl radical bonded to a nitrogen atom through a tertiary carbon atom means that the tertiary carbon atom is a member of the alicyclic radical and is bonded to three other non-hydrogen atoms, such as to three carbon atoms. Examples of such radicals include 1-adamantyl, 3-noradamantyl, 1-norbornyl, 1-triptycenyl, 1-tricyclo[5.2.1.02,6]decyl, 4-tricyclo[2.2.1.02,6]heptyl, and the like. The term xe2x80x9chydrocarbylxe2x80x9d means a radical derived from a hydrocarbon. Preferred hydrocarbyl radicals are those containing from 1-20 carbon atoms. Examples of such radicals include alkyl, aryl, cycloalkyl radicals or combinations thereof. Preferred radicals are C1-C20 alkyl, C6-C22 aryl, and C3-C20 cycloalkyl radicals, or combinations thereof.
A more preferred class of compounds are those compounds represented by the above Formula IV wherein M is Ti. A most preferred class of compounds are those represented by the above Formula IV wherein M is Ti and wherein R1 and R2 are independently selected from C1-C6 alkyl radicals, C6-C12 aryl radicals, C3-C12 cycloalkyl radicals, and combinations thereof.
Examples of specific compounds within the classes of compounds defined by Formula IV include:
dimethylsilyl(tetramethylcyclopentadienyl)-(1-adamantylamido)titanium dimethyl;
dimethylsilyl(tetramethylcyclopentadienyl)-(3-noradamantantylamido)titanium dimethyl;
dimethylsily(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantylamido)titanium dimethyl;
dimethylsilyl(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamido)titanium dimethyl;
dimethylsilyl(tetramethylcyclopentadienyl)-(4-tricyclo[2.2.1.02,6]heptylamido)titanium dimethyl;
dimethylsilyl(tetramethylcyclopentadienyl)-(3-methyl-1-adamantyl)titanium dimethyl;
dimethylsilyl(tetramethylcyclopentadienyl)-(3,5,7-trimethyladamantyl)titanium dimethyl;
methylphenylsilyl(tetramethylcyclopentadienyl)-(1-adamantylamido)titanium dimethyl;
methylphenylsilyl(tetramethylcyclopentadienyl)-(3-noradamantantylamido)titanium dimethyl;
methylphenylsilyl(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantylamido)titanium dimethyl;
methylphenylsilyl(tetramethylcyclopentadienyl)-(3-methyl-adamantylamido)titanium dimethyl
methylphenylsilyl(tetramethylcyclopentadienyl)-(3,5,7-trimethyladamantylamido)titanium dimethyl
methylphenylsilyl(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamido)titanium dimethyl;
methylphenylsilyl(tetramethylcyclopentadienyl)-(4-tricyclo[2.2.1.02,6]heptylamido)titanium dimethyl;
diphenylsilyl(tetramethylcyclopentadienyl)-(1-adamantylamido)titanium dimethyl;
diphenylsilyl(tetramethylcyclopentadienyl)-(3-noradamantanylamido)titanium dimethyl;
diphenylsilyl(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantylamido)titanium dimethyl;
diphenylsilyl(tetramethylcyclopentadienyl)-(3-methyl-1-adamantylamido)titanium dimethyl;
diphenylsilyl(tetramethylcyclopentadienyl)-(3,5,7 trimethyl-1-adamantylamido)titanium dimethyl;
diphenylsilyl(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamido)titanium dimethyl;
diphenylsilyl(tetramethylcyclopentadienyl)-(4-tricyclo[2.2.1.02,6]heptylamido)titanium dimethyl;
dimethylsilyl(tetramethylcyclopentadienyl)-(1-adamantylamido)titanium diphenyl;
dimethylsilyl(tetramethylcyclopentadienyl)-(3-noradamantanylamido)titanium diphenyl;
dimethylsilyl(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantylamido)titanium diphenyl;
dimethylsilyl(tetramethylcyclopentadienyl)-(3-methyl-1-adamantylamido)titanium diphenyl;
dimethylsilyl(tetramethylcyclopentadienyl)-(3,5,7-trimethyl-1-adamantylamido)titanium diphenyl;
dimethylsilyl(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamido)titanium diphenyl;
dimethylsilyl(tetramethylcyclopentadienyl)-(4-tricyclo[2.2.1.02,6]heptylamido)titanium diphenyl;
methylphenylsilyl(tetramethylcyclopentadienyl)-(1-adamantylamido)titanium diphenyl;
methylphenylsilyl(tetramethylcyclopentadienyl)-(3-noradamantanylamido)titanium diphenyl;
methylphenylsilyl(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantylamido)titanium diphenyl;
methylphenylsilyl(tetramethylcyclopentadienyl)-(3-methyl-1-adamantylamido)titanium diphenyl;
methylphenylsilyl(tetramethylcyclopentadienyl)-(3,5,7-trimethyl-1-adamantylamido)titanium diphenyl;
methylphenylsilyl(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamido)titanium diphenyl;
methylphenylsilyl(tetramethylcyclopentadienyl)-(4-tricyclo[2.2.1.02,6]heptylamido)titanium diphenyl;
diphenylsilyl(tetramethylcyclopentadienyl)-(1-adamantylamido)titanium diphenyl;
diphenylsilyl(tetramethylcyclopentadienyl)-(3-noradamantanylamido)titanium diphenyl;
diphenylsilyl(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantylamido)titanium diphenyl;
diphenylsilyl(tetramethylcyclopentadienyl)-(3-methyl-1-adamantylamido)titanium diphenyl;
diphenylsilyl(tetramethylcyclopentadienyl)-(3,5,7-trimethyl-1-adamantylamido)titanium diphenyl;
diphenylsilyl(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamido)titanium diphenyl;
diphenylsilyl(tetramethylcyclopentadienyl)-(4-tricyclo[2.2.1.02,6]heptylamido)titanium diphenyl;
dimethylsilyl(tetramethylcyclopentadienyl)-(1-adamantylamido)hafnium dimethyl;
dimethylsilyl(tetramethylcyclopentadienyl)-(3-noradamantanylamido)hafnium dimethyl;
dimethylsilyl(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantylamido)hafnium dimethyl;
dimethylsilyl(tetramethylcyclopentadienyl)-(3-methyl-1-adamantylamido)hafnium dimethyl;
dimethylsilyl(tetramethylcyclopentadienyl)-(3,5,7-trimethyl-1-adamantylamido)hafnium dimethyl;
dimethylsilyl(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamido)hafnium dimethyl;
dimethylsilyl(tetramethylcyclopentadienyl)-(4-tricyclo[2.2.1.02,6]heptylamido)hafnium dimethyl;
methylphenylsilyl(tetramethylcyclopentadienyl)-(1-adamantylamido)hafnium dimethyl;
methylphenylsilyl(tetramethylcyclopentadienyl)-(3-noradamantanylamido)hafnium dimethyl;
methylphenylsilyl(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantylamido)hafnium dimethyl;
methylphenylsilyl(tetramethylcyclopentadienyl)-(3-methyl-1-adamantylamido)hafnium dimethyl;
methylphenylsilyl(tetramethylcyclopentadienyl)-(3,5,7-trimethyl-1-adamantylamido)hafnium dimethyl;
methylphenylsilyl(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamido)hafnium dimethyl;
methylphenylsilyl(tetramethylcyclopentadienyl)-(4-tricyclo[2.2.1.02,6]heptylamido)hafnium dimethyl;
diphenylsilyl(tetramethylcyclopentadienyl)-(1-adamantylamido)hafnium dimethyl;
diphenylsilyl(tetramethylcyclopentadienyl)-(3-noradamantanylamido)hafnium dimethyl;
diphenylsilyl(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantylamido)hafnium dimethyl;
diphenylsilyl(tetramethylcyclopentadienyl)-(3-methyl-1-adamantylamido)hafnium dimethyl;
diphenylsilyl(tetramethylcyclopentadienyl)-(3,5,7-trimethyl-1-adamantylamido)hafnium dimethyl;
diphenylsilyl(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamido)hafnium dimethyl;
diphenylsilyl(tetramethylcyclopentadienyl)-(4-triclo[2.2.1.02,6]heptylamido)hafnium dimethyl;
dimethylsilyl(tetramethylcyclopentadienyl)-(1-adamantylamido)hafnium diphenyl;
dimethylsilyl(tetramethylcyclopentadienyl)-(3-noradamantanylamido)hafnium diphenyl;
dimethylsilyl(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantylamido)hafnium diphenyl;
dimethylsilyl(tetramethylcyclopentadienyl)-(3-methyl-1-adamantylamido)hafnium diphenyl;
dimethylsilyl(tetramethylcyclopentadienyl)-(3,5,7-trimethyl-1-adamantylamido)hafnium diphenyl;
dimethylsilyl(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamido)hafnium diphenyl;
dimethylsilyl(tetramethylcyclopentadienyl)-(4-tricyclo[2.2.1.02,6]heptylamido)hafnium diphenyl;
methylphenylsilyl(tetramethylcyclopentadienyl)-(1-adamantylamido)hafnium diphenyl;
methylphenylsilyl(tetramethylcyclopentadienyl)-(3-noradamantanylamido)hafnium diphenyl;
methylphenylsilyl(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantylamido)hafnium diphenyl;
methylphenylsilyl(tetramethylcyclopentadienyl)-(3-methyl-1-adamantylamido)hafnium diphenyl;
methylphenylsilyl(tetramethylcyclopentadienyl)-(3,5,7-trimethyl-1-adamantylamido)hafnium diphenyl;
methylphenylsilyl(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamido)hafnium diphenyl;
methylphenylsilyl(tetramethylcyclopentadienyl)-(4-tricyclo[2.2.1.02,6]heptylamido)hafnium diphenyl;
diphenylsilyl(tetramethylcyclopentadienyl)-(1-adamantylamido)hafnium diphenyl;
diphenylsilyl(tetramethylcyclopentadienyl)-(3-noradamantanylamido)hafnium diphenyl;
diphenylsilyl(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantylamido)hafnium diphenyl;
diphenylsily(tetramethylcyclopentadienyl)-(3-methyl-1-adamantylamido)hafnium diphenyl;
diphenylsilyl(tetramethylcyclopentadienyl)-(3,5,7-trimethyl-1-adamantylamido)hafnium diphenyl;
diphenylsilyl(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamido)hafnium diphenyl;
diphenylsilyl(tetramethylcyclopentadienyl)-(4-tricyclo[2.2.1.02,6]heptylamido)hafnium diphenyl;
dimethylsilyl(tetramethylcyclopentadienyl)-(1-adamantylamido)zirconium dimethyl;
dimethylsilyl(tetramethylcyclopentadienyl)-(3-noradamantanylamido)zirconium dimethyl;
dimethylsilyl(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantylamido)zirconium dimethyl;
dimethylsilyl(tetramethylcyclopentadienyl)-(3-methyl-1-adamantylamido)zirconium dimethyl;
dimethylsilyl(tetramethylcyclopentadienyl)-(3,5,7-trimethyl-1-adamantylamido)zirconium dimethyl;
dimethylsilyl(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamido)zirconium dimethyl;
dimethylsilyl(tetramethylcyclopentadienyl)-(4-tricyclo[2.2.1.02,6]heptylamido)zirconium dimethyl;
methylphenylsilyl(tetramethylcyclopentadienyl)-(1-adamantylamido)zirconium dimethyl;
methylphenylsilyl(tetramethylcyclopentadienyl)-(3-noradamantanylamido)zirconium dimethyl;
methylphenylsilyl(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantylamido)zirconium dimethyl;
methylphenylsilyl(tetramethylcyclopentadienyl)-(3-methyl-1-adamantylamido)zirconium dimethyl;
methylphenylsilyl(tetramethylcyclopentadienyl)-(3,5,7-trimethyl-1-adamantylamido)zirconium dimethyl;
methylphenylsilyl(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamido)zirconium dimethyl;
methylphenylsilyl(tetramethylcyclopentadienyl)-(4-tricyclo[2.2.1.02,6]heptylamido)zirconium dimethyl;
diphenylsilyl(tetramethylcyclopentadienyl)-(1-adamantylamido)zirconium dimethyl;
diphenylsilyl(tetramethylcyclopentadienyl)-(3-noradamantanylamido)zirconium dimethyl;
diphenylsilyl(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantylamido)zirconium dimethyl;
diphenylsilyl(tetramethylcyclopentadienyl)-(3-methyl-1-adamantylamido)zirconium dimethyl;
diphenylsilyl(tetramethylcyclopentadienyl)-(3,5,7-trimethyl-1-adamantylamido)zirconium dimethyl;
diphenylsilyl(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamido)zirconium dimethyl;
diphenylsilyl(tetramethylcyclopentadienyl)-(4-tricyclo[2.2.1.02,6]heptylamido)zirconium dimethyl;
dimethylsilyl(tetramethylcyclopentadienyl)-(1-adamantylamido)zirconium diphenyl;
dimethylsilyl(tetramethylcyclopentadienyl)-(3-noradamantanylamido)zirconium diphenyl;
dimethylsilyl(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantylamido)zirconium diphenyl;
dimethylsilyl(tetramethylcyclopentadienyl)-(3-methyl-1-adamantylamido)zirconium diphenyl;
dimethylsilyl(tetramethylcyclopentadienyl)-(3,5,7-trimethyl-1-adamantylamido)zirconium diphenyl;
dimethylsilyl(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamido)zirconium diphenyl;
dimethylsilyl(tetramethylcyclopentadienyl)-(4-tricyclo[2.2.1.02,6]heptylamido)zirconium diphenyl;
methylphenylsilyl(tetramethylcyclopentadienyl)-(1-adamantylamido)zirconium diphenyl;
methylphenylsilyl(tetramethylcyclopentadienyl)-(3-noradamantanylamido)zirconium diphenyl;
methylphenylsilyl(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantylamido)zirconium diphenyl;
methylphenylsilyl(tetramethylcyclopentadienyl)-(3-methyl-1-adamantylamido)zirconium diphenyl;
methylphenylsilyl(tetramethylcyclopentadienyl)-(3,5,7-trimethyl-1-adamantylamido)zirconium diphenyl;
methylphenylsilyl(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamido)zirconium diphenyl;
methylphenylsilyl(tetramethylcyclopentadienyl)-(4-tricyclo[2.2.1.02,6]heptylamido)zirconium diphenyl;
diphenylsilyl(tetramethylcyclopentadienyl)-(1-adamantylamido)zirconium diphenyl;
diphenylsilyl(tetramethylcyclopentadienyl)-(3-noradamantanylamido)zirconium diphenyl;
diphenylsilyl(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantylamido)zirconium diphenyl;
diphenylsilyl(tetramethylcyclopentadienyl)-(3-methyl-1-adamantylamido)zirconium diphenyl;
diphenylsilyl(tetramethylcyclopentadienyl)-(3,5,7-trimethyl-1-adamantylamido)zirconium diphenyl;
diphenylsilyl(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamido)zirconium diphenyl;
diphenylsilyl(tetramethylcyclopentadienyl)-(4-tricyclo[2.2.1.02,6]heptylamido)zirconium diphenyl;
dimethylgermanyl(tetramethylcyclopentadienyl)-(1-adamantylamido)titanium dimethyl;
dimethylgermanyl(tetramethylcyclopentadienyl)-(3-noradamantantylamido)titanium dimethyl;
dimethylgermanyl(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantylamido)titanium dimethyl;
dimethylgermanyl(tetramethylcyclopentadienyl)-(3-methyl-1-adamantylamido)titanium dimethyl;
dimethylgermanyl(tetramethylcyclopentadienyl)-(3,5,7-trimethyl-1-adamantylamido)titanium dimethyl;
dimethylgermanyl(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamido)titanium dimethyl;
dimethylgermanyl(tetramethylcyclopentadienyl)-(4-tricyclo[2.2.1.02,6]heptylamido)titanium dimethyl;
methylphenylgermanyl(tetramethylcyclopentadienyl)-(1-adamantylamido) titanium dimethyl;
methylphenylgermanyl(tetramethylcyclopentadienyl)-(3-noradamantantylamido)titanium dimethyl;
methylphenylgermanyl(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantylamido)titanium dimethyl;
methylphenylgermanyl(tetramethylcyclopentadienyl)-(3-methyl-1-adamantylamido)titanium dimethyl;
methylphenylgermanyl(tetramethylcyclopentadienyl)-(3,5,7-trimethyl-1-adamantylamido)titanium dimethyl;
methylphenylgermanyl(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamido)titanium dimethyl;
methylphenylgermanyl(tetramethylcyclopentadienyl)-(4-tricyclo[2.2.1.02,6]heptylamido)titanium dimethyl;
diphenylgermanyl(tetramethylcyclopentadienyl)-(1-adamantylamido)titanium dimethyl;
diphenylgermanyl(tetramethylcyclopentadienyl)-(3-noradamantanylamido)titanium dimethyl;
diphenylgermanyl(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantylamido)titanium dimethyl;
diphenylgermanyl(tetramethylcyclopentadienyl)-(3-methyl-1-adamantylamido)titanium dimethyl;
diphenylgermanyl(tetramethylcyclopentadienyl)-(3,5,7-trimethyl-1-adamantylamido)titanium dimethyl;
diphenylgermanyl(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamido)titanium dimethyl;
diphenylgermanyl(tetramethylcyclopentadienyl)-(4-tricyclo[2.2.1.02,6]heptylamido)titanium dimethyl;
dimethylgermanyl(tetramethylcyclopentadienyl)-(1-adamantylamido)titanium diphenyl;
dimethylgermanyl(tetramethylcyclopentadienyl)-(3-noradamantanylamido)titanium diphenyl;
dimethylgermanyl(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantylamido)titanium diphenyl;
dimethylgermanyl(tetramethylcyclopentadienyl)-(3-methyl-1-adamantylamido)titanium diphenyl;
dimethylgermanyl(tetramethylcyclopentadienyl)-(3,5,7-trimethyl-1-adamantylamido)titanium diphenyl;
dimethylgermanyl(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamido)titanium diphenyl;
dimethylgermanyl(tetramethylcyclopentadienyl)-(4-tricyclo[2.2.1.02,6]heptylamido)titanium diphenyl;
methylphenylgermanyl(tetramethylcyclopentadienyl)-(1-adamantylamido)titanium diphenyl;
methylphenylgermanyl(tetramethylcyclopentadienyl)-(3-noradamantanylamido)titanium diphenyl;
methylphenylgermanyl(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantylamido)titanium diphenyl;
methylphenylgermanyl(tetramethylcyclopentadienyl)-(3-methyl-1-adamantylamido)titanium diphenyl;
methylphenylgermanyl(tetramethylcyclopentadienyl)-(3,5,7-trimethyl-1-adamantylamido)titanium diphenyl;
methylphenylgermanyl(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamido)titanium diphenyl;
methylphenylgermanyl(tetramethylcyclopentadienyl)-(4-tricyclo[2.2.1.02,6]heptylamido)titanium diphenyl;
diphenylgermanyl(tetramethylcyclopentadienyl)-(1-adamantylamido)titanium diphenyl;
diphenylgermanyl(tetramethylcyclopentadienyl)-(3-noradamantanylamido)titanium diphenyl;
diphenylgermanyl(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantylamido)titanium diphenyl;
diphenylgermanyl(tetramethylcyclopentadienyl)-(3-methyl-1-adamantylamido)titanium diphenyl;
diphenylgermanyl(tetramethylcyclopentadienyl)-(3,5,7-trimethyl-1-adamantylamido)titanium diphenyl;
diphenylgermanyl(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamido)titanium diphenyl;
diphenylgermanyl(tetramethylcyclopentadienyl)-(4-tricyclo[2.2.1.02,6]heptylamido)titanium diphenyl;
dimethylgermanyl(tetramethylcyclopentadienyl)-(1-adamantylamido)hafnium dimethyl;
dimethylgermanyl(tetramethylcyclopentadienyl)-(3-noradamantanylamido)hafnium dimethyl;
dimethylgermanyl(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantylamido)hafnium dimethyl;
dimethylgermanyl(tetramethylcyclopentadienyl)-(3-methyl-1-adamantylamido)hafnium dimethyl;
dimethylgermanyl(tetramethylcyclopentadienyl)-(3,5,7-trimethyl-1-adamantylamido)hafnium dimethyl;
dimethylgermanyl(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamido)hafnium dimethyl;
dimethylgermanyl(tetramethylcyclopentadienyl)-(4-tricyclo[2.2.1.02,6]heptylamido)titanium diphenyl;
methylphenylgermanyl(tetramethylcyclopentadienyl)-(1-adamantylamido)hafnium dimethyl;
methylphenylgermanyl(tetramethylcyclopentadienyl)-(3-noradamantanylamido)hafnium dimethyl;
methylphenylgermanyl(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantylamido)hafnium dimethyl;
methylphenylgermanyl(tetramethylcyclopentadienyl)-(3-methyl-1-adamantylamido)hafnium dimethyl;
methylphenylgermanyl(tetramethylcyclopentadienyl)-(3,5,7-trimethyl-1-adamantylamido)hafnium dimethyl;
methylphenylgermanyl(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamido)hafnium dimethyl;
methylphenylgermanyl(tetramethylcyclopentadienyl)-(4-tricyclo[2.2.1.02,6]heptylamido)hafnium dimethyl;
diphenylgermanyl(tetramethylcyclopentadienyl)-(1-adamantylamido)hafnium dimethyl;
diphenylgermanyl(tetramethylcyclopentadienyl)-(3-noradamantanylamido)hafnium dimethyl;
diphenylgermanyl(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantylamido)hafnium dimethyl;
diphenylgermanyl(tetramethylcyclopentadienyl)-(3-methyl-1-adamantylamido)hafnium dimethyl;
diphenylgermanyl(tetramethylcyclopentadienyl)-(3,5,7-trimethyl-1-adamantylamido)hafnium dimethyl;
diphenylgermanyl(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamido)hafnium dimethyl;
diphenylgermanyl(tetramethylcyclopentadienyl)-(4-tricyclo[2.2.1.02,6]heptylamido)hafnium dimethyl;
dimethylgermanyl(tetramethylcyclopentadienyl)-(1-adamantylamido)hafnium diphenyl;
dimethylgermanyl(tetramethylcyclopentadienyl)-(3-noradamantanylamido)hafnium diphenyl;
dimethylgermanyl(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantylamido)hafnium diphenyl;
dimethylgermanyl(tetramethylcyclopentadienyl)-(3-methyl-1-adamantylamido)hafnium diphenyl;
dimethylgermanyl(tetramethylcyclopentadienyl)-(3,5,7-trimethyl-1-adamantylamido)hafnium diphenyl;
dimethylgermanyl(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamido)hafnium diphenyl;
dimethylgermanyl(tetramethylcyclopentadienyl)-(4-tricyclo[2.2.1.02,6]heptylamido)hafnium diphenyl;
methylphenylgermanyl(tetramethylcyclopentadienyl)-(1-adamantylamido)hafnium diphenyl;
methylphenylgermanyl(tetramethylcyclopentadienyl)-(3-noradamantanylamido)hafnium diphenyl;
methylphenylgermanyl(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantylamido)hafnium diphenyl;
methylphenylgermanyl(tetramethylcyclopentadienyl)-(3-methyl-1-adamantylamido)hafnium diphenyl;
methylphenylgermanyl(tetramethylcyclopentadienyl)-(3,5,7-trimethyl-1-adamantylamido)hafnium diphenyl;
methylphenylgermanyl(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamido)hafnium diphenyl;
methylphenylgermanyl(tetramethylcyclopentadienyl)-(4-tricyclo[2.2.1.02,6]heptylamido)hafnium diphenyl;
diphenylgermanyl(tetramethylcyclopentadienyl)-(1-adamantylamido)hafnium diphenyl;
diphenylgermanyl(tetramethylcyclopentadienyl)-(3-noradamantanylamido)hafnium diphenyl;
diphenylgermanyl(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantylamido)hafnium diphenyl;
diphenylgermanyl(tetramethylcyclopentadienyl)-(3-methyl-1-adamantylamido)hafnium diphenyl;
diphenylgermanyl(tetramethylcyclopentadienyl)-(3,5,7-trimethyl-1-adamantylamido)hafnium diphenyl;
diphenylgermanyl(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamido)hafnium diphenyl;
diphenylgermanyl(tetramethylcyclopentadienyl)-(4-tricyclo[2.2.1.02,6]heptylamido)hafnium diphenyl;
dimethylgermanyl(tetramethylcyclopentadienyl)-(1-adamantylamido)zirconium dimethyl;
dimethylgermanyl(tetramethylcyclopentadienyl)-(3-noradamantanylamido)zirconium dimethyl;
dimethylgermanyl(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantylamido)zirconium dimethyl;
dimethylgermanyl(tetramethylcyclopentadienyl)-(3-methyl-1-adamantylamido)zirconium dimethyl;
dimethylgermanyl(tetramethylcyclopentadienyl)-(3,5,7-trimethyl-1-adamantylamido)zirconium dimethyl;
dimethylgermanyl(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamido)zirconium dimethyl;
dimethylgermanyl(tetramethylcyclopentadienyl)-(4-tricyclo[2.2.1.02,6]heptylamido)zirconium dimethyl;
methylphenylgermanyl(tetramethylcyclopentadienyl)-(1-adamantylamido)zirconium dimethyl;
methylphenylgermanyl(tetramethylcyclopentadienyl)-(3-noradamantanylamido)zirconium dimethyl;
methylphenylgermanyl(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantylamido)zirconium dimethyl;
methylphenylgermanyl(tetramethylcyclopentadienyl)-(3-methyl-1-adamantylamido)zirconium dimethyl;
methylphenylgermanyl(tetramethylcyclopentadienyl)-(3,5,7-trimethyl-1-adamantylamido)zirconium dimethyl;
methylphenylgermanyl(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamido)zirconium dimethyl;
methylphenylgermanyl(tetramethylcyclopentadienyl)-(4-tricyclo[2.2.1.02,6]heptylamido)zirconium dimethyl;
diphenylgermanyl(tetramethylcyclopentadienyl)-(1-adamantylamido)zirconium dimethyl;
diphenylgermanyl(tetramethylcyclopentadienyl)-(3-noradamantanylamido)zirconium dimethyl;
diphenylgermanyl(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantylamido)zirconium dimethyl;
diphenylgermanyl(tetramethylcyclopentadienyl)-(3-methyl-1-adamantylamido)zirconium dimethyl;
diphenylgermanyl(tetramethylcyclopentadienyl)-(3,5,7-trimethyl-1-adamantylamido)zirconium dimethyl;
diphenylgermanyl(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamido)zirconium dimethyl;
diphenylgermanyl(tetramethylcyclopentadienyl)-(4-tricyclo[2.2.1.02,6]heptylamido)zirconium dimethyl;
dimethylgermanyl(tetramethylcyclopentadienyl)-(1-adamantylamido)zirconium diphenyl;
dimethylgermanyl(tetramethylcyclopentadienyl)-(3-noradamantanylamido)zirconium diphenyl;
dimethylgermanyl(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantylamido)zirconium diphenyl;
dimethylgermanyl(tetramethylcyclopentadienyl)-(3-methyl-1-adamantylamido)zirconium diphenyl;
dimethylgermanyl(tetramethylcyclopentadienyl)-(3,5,7-trimethyl-1-adamantylamido)zirconium diphenyl;
dimethylgermanyl(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamido)zirconium diphenyl;
dimethylgermanyl(tetramethylcyclopentadienyl)-(4-tricyclo[2.2.1.02,6]heptylamido)zirconium diphenyl;
methylphenylgermanyl(tetramethylcyclopentadienyl)-(1-adamantylamido)zirconium diphenyl;
methylphenylgermanyl(tetramethylcyclopentadienyl)-(3-noradamantanylamido)zirconium diphenyl;
methylphenylgermanyl(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantylamido)zirconium diphenyl;
methylphenylgermanyl(tetramethylcyclopentadienyl)-(3-methyl-1-adamantylamido)zirconium diphenyl;
methylphenylgermanyl(tetramethylcyclopentadienyl)-(3,5,7-trimethyl-1-adamantylamido)zirconium diphenyl;
methylphenylgermanyl(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamido)zirconium diphenyl;
methylphenylgermanyl(tetramethylcyclopentadienyl)-(4-tricyclo[2.2.1.02,6]heptylamido)zirconium diphenyl;
diphenylgermanyl(tetramethylcyclopentadienyl)-(1-adamantylamido)zirconium diphenyl;
diphenylgermanyl(tetramethylcyclopentadienyl)-(3-noradamantanylamido)zirconium diphenyl;
diphenylgermanyl(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantylamido)zirconium diphenyl;
diphenylgermanyl(tetramethylcyclopentadienyl)-(3-methyl-1-adamantylamido)zirconium diphenyl;
diphenylgermanyl(tetramethylcyclopentadienyl)-(3,5,7-trimethyl-1-adamantylamido)zirconium diphenyl;
diphenylgermanyl(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamido)zirconium diphenyl;
diphenylgermanyl(tetramethylcyclopentadienyl)-(4-tricyclo[2.2.1.02,6]heptylamido)zirconium diphenyl;
The above specific examples wherein each Q is methyl or each Q is phenyl is prepared from the corresponding compound wherein each Q is chloro. The dichloro (both Q are Cl) species of each of the above compounds are also within Formula II.
Another preferred class of compounds of the present invention are those compounds represented by the formula: 
wherein R3, R4, Q, M, u, w, x, and L are as defined above; wherein T is selected from radicals of the formula (CR5R6)y wherein R5 and R6 are independently selected from hydrogen and C1-C20 hydrocarbyl radicals; and wherein y is 1, 2, or 3.
A more preferred class of compounds are those compounds represented by the above Formula V wherein M is Ti. A most preferred class of compounds are those represented by the above Formula V wherein M is Ti and wherein R5 and R6 are independently selected from hydrogen, C1-C6 alkyl radicals, C6-C12 aryl radicals, C3-C12 cycloalkyl radicals and combinations thereof.
Examples of specific compounds within the class of compounds defined by Formula V include:
methylene(tetramethylcyclopentadienyl)-(1-adamantylamido)titanium dimethyl;
methylene(tetramethylcyclopentadienyl)-(3-noradamantanylamido)titanium dimethyl;
methylene(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantylamido)titanium dimethyl;
methylene(tetramethylcyclopentadienyl)-(3-methyl-1-adamantylamido)titanium dimethyl;
methylene(tetramethylcyclopentadienyl)-(3,5,7-trimethyl-1-adamantylamido)titanium dimethyl;
methylene(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamido)titanium dimethyl;
methylene(tetramethylcyclopentadienyl)-(4-tricyclo[2.2.1.02,6]heptylamido)titanium dimethyl;
dimethylmethylene(tetramethylcyclopentadienyl)-(1-adamantylamido)titanium dimethyl;
dimethylmethylene(tetramethylcyclopentadienyl)-(3-noradamantanylamido)titanium dimethyl;
dimethylmethylene(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantylamido)titanium dimethyl;
dimethylmethylene(tetramethylcyclopentadienyl)-(3-methyl-1-adamantylamido)titanium dimethyl;
dimethylmethylene(tetramethylcyclopentadienyl)-(3,5,7-trimethyl-1-adamantylamido)titanium dimethyl;
dimethylmethylene(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamido)titanium dimethyl;
dimethymethylene(tetramethylcyclopentadienyl)-(4-tricyclo[2.2.1.02,6]heptylamido)titanium dimethyl;
diethylmethylene(tetramethylcyclopentadienyl)-(1-adamantylamido)titanium dimethyl;
diethylmethylene(tetramethylcyclopentadienyl)-(3-noradamantanylamido)titanium dimethyl;
diethylmethylene(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantylamido)titanium dimethyl;
diethylmethylene(tetramethylcyclopentadienyl)-(3-methyl-1-adamantylamido)titanium dimethyl;
diethylmethylene(tetramethylcyclopentadienyl)-(3,5,7-trimethyl-1-adamantylamido)titanium dimethyl;
diethylmethylene(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamido)titanium dimethyl;
diethylmethylene(tetramethylcyclopentadienyl)-(4-tricyclo[2.2.1.02,6]heptylamido)titanium dimethyl;
ethylene(tetramethylcyclopentadienyl)-(1-adamantylamido)titanium dimethyl;
ethylene(tetramethylcyclopentadienyl)-(3-noradamantanylamido)titanium dimethyl;
ethylene(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantylamido)titanium dimethyl;
ethylene(tetramethylcyclopentadienyl)-(3-methyl-1-adamantylamido)titanium dimethyl;
ethylene(tetramethylcyclopentadienyl)-(3,5,7-trimethyl-1-adamantylamido)titanium dimethyl;
ethylene(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamido)titanium dimethyl;
ethylene(tetramethylcyclopentadienyl)-(4-tricyclo[2.2.1.02,6]heptylamido)titanium dimethyl;
1,1-dimethylethylene(tetramethylcyclopentadienyl)-(1-adamantylamido)titanium dimethyl;
1,1-dimethylethylene(tetramethylcyclopentadienyl)-(3-noradamantanylamido)titanium dimethyl;
1,1-dimethylethylene(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantylamido)titanium dimethyl;
1,1-dimethylethylene(tetramethylcyclopentadienyl)-(3-methyl-1-adamantylamido)titanium dimethyl;
1,1-dimethylethylene(tetramethylcyclopentadienyl)-(3,5,7-trimethyl-1-adamantylamido)titanium dimethyl;
1,1-dimethylethylene(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamido)titanium dimethyl;
1,1-dimethylethylene(tetramethylcyclopentadienyl)-(4-tricyclo[2.2.1.02,6]heptylamido)titanium dimethyl;
1,1-dipropylethylene(tetramethylcyclopentadienyl)-(1-adamantylamido)titanium dimethyl;
1,1-dipropylethylene(tetramethylcyclopentadienyl)-(3-noradamantanylamido)titanium dimethyl;
1,1-dipropylethylene(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantylamido)titanium dimethyl;
1,1-dipropylethylene(tetramethylcyclopentadienyl)-(3-methyl-1-adamantylamido)titanium dimethyl;
1,1-dipropylethylene(tetramethylcyclopentadienyl)-(3,5,7-trimethyl-1-adamantylamido)titanium dimethyl;
1,1-dipropylethylene(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamido)titanium dimethyl;
1,1-dipropylethylene(tetramethylcyclopentadienyl)-(4-tricyclo[2.2.1.02,6]heptylamido)titanium dimethyl;
1,2-dimethylethylene(tetramethylcyclopentadienyl)-(1-adamantylamido)titanium dimethyl;
1,2-dimethylethylene(tetramethylcyclopentadienyl)-(3-noradamantanylamido)titanium dimethyl;
1,2-dimethylethylene(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantylamido)titanium dimethyl;
1,2-dimethylethylene(tetramethylcyclopentadienyl)-(3-methyl-1-adamantylamido)titanium dimethyl;
1,2-dimethylethylene(tetramethylcyclopentadienyl)-(3,5,7-trimethyl-1-adamantylamido)titanium dimethyl;
1,2-dimethylethylene(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamido)titanium dimethyl;
1,2-dimethylethylene(tetramethylcyclopentadienyl)-(4-tricyclo[2.2.1.02,6]heptylamido)titanium dimethyl;
1,2-dipropylethylene(tetramethylcyclopentadienyl)-(1-adamantylamido)titanium dimethyl;
1,2-dipropylethylene(tetramethylcyclopentadienyl)-(3-noradamantanylamido)titanium dimethyl;
1,2-dipropylethylene(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantylamido)titanium dimethyl;
1,2-dipropylethylene(tetramethylcyclopentadienyl)-(3-methyl-1-adamantylamido)titanium dimethyl;
1,2-dipropylethylene(tetramethylcyclopentadienyl)-(3,5,7-trimethyl-1-adamantylamido)titanium dimethyl;
1,2-dipropylethylene(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamido)titanium dimethyl;
1,2-dipropylethylene(tetramethylcyclopentadienyl)-(4-tricyclo[2.2.1.02,6]heptylamido)titanium dimethyl;
2,2-dimethylethylene(tetramethylcyclopentadienyl)-(1-adamantylamido)titanium dimethyl;
2,2-dimethylethylene(tetramethylcyclopentadienyl)-(3-noradamantanylamido)titanium dimethyl;
2,2-dimethylethylene(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantylamido)titanium dimethyl;
2,2-dimethylethylene(tetramethylcyclopentadienyl)-(3-methyl-1-adamantylamido)titanium dimethyl;
2,2-dimethylethylene(tetramethylcyclopentadienyl)-(3,5,7-trimethyl-1-adamantylamido)titanium dimethyl;
2,2-dimethylethylene(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamido)titanium dimethyl;
2,2-dimethylethylene(tetramethylcyclopentadienyl)-(4-tricyclo[2.2.1.02,6]heptylamido)titanium dimethyl;
2,2-dipropylethylene(tetramethylcyclopentadienyl)-(1-adamantylamido)titanium dimethyl;
2,2-dipropylethylene(tetramethylcyclopentadienyl)-(3-noradamantanylamido)titanium dimethyl;
2,2-dipropylethylene(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantylamido)titanium dimethyl;
2,2-dipropylethylene(tetramethylcyclopentadienyl)-(3-methyl-1-adamantylamido)titanium dimethyl;
2,2-dipropylethylene(tetramethylcyclopentadienyl)-(3,5,7-trimethyl-1-adamantylamido)titanium dimethyl;
2,2-dipropylethylene(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamido)titanium dimethyl;
2,2-dipropylethylene(tetramethylcyclopentadienyl)-(4-tricyclo[2.2.1.02,6]heptylmido)titanium dimethyl;
1,1-diphenylethylene(tetramethylcyclopentadienyl)-(1-adamantylamido)titanium dimethyl;
1,1-diphenylethylene(tetramethylcyclopentadienyl)-(3-noradamantanylamido)titanium dimethyl;
1,1-diphenylethylene(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantylamido)titanium dimethyl;
1,1-diphenylethylene(tetramethylcyclopentadienyl)-(3-methyl-1-adamantylamido)titanium dimethyl;
1,1-diphenylethylene(tetramethylcyclopentadienyl)-(3,5,7-trimethyl-1-adamantylamido)titanium dimethyl;
1,1-diphenylethylene(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamido)titanium dimethyl;
1,1-diphenylethylene(tetramethylcyclopentadienyl)-(4-tricyclo[2.2.1.02,6]heptylamido)titanium dimethyl;
1,2-diphenylethylene(tetramethylcyclopentadienyl)-(1-adamantylamido)titanium dimethyl;
1,2-diphenylethylene(tetramethylcyclopentadienyl)-(3-noradamantanylamido)titanium dimethyl;
1,2-diphenylethylene(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantylamido)titanium dimethyl;
1,2-diphenylethylene(tetramethylcyclopentadienyl)-(3-methyl-1-adamantylamido)titanium dimethyl;
1,2-diphenylethylene(tetramethylcyclopentadienyl)-(3,5,7-trimethyl-1-adamantylamido)titanium dimethyl;
1,2-diphenylethylene(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamido)titanium dimethyl;
1,2-diphenylethylene(tetramethylcyclopentadienyl)-(4-tricyclo[2.2.1.02,6]heptylamido)titanium dimethyl;
2,2-diphenylethylene(tetramethylcyclopentadienyl)-(1-adamantylamido)titanium dimethyl;
2,2-diphenylethylene(tetramethylcyclopentadienyl)-(3-noradamantanylamido)titanium dimethyl;
2,2-diphenylethylene(tetramethylcyclopentadienyl)-(3,5-dimethyl-1-adamantylamido)titanium dimethyl;
2,2-diphenylethylene(tetramethylcyclopentadienyl)-(3-methyl-1-adamantylamido)titanium dimethyl;
2,2-diphenylethylene(tetramethylcyclopentadienyl)-(3,5,7-trimethyl-1-adamantylamido)titanium dimethyl;
2,2-diphenylethylene(tetramethylcyclopentadienyl)-(3-fluoro-1-adamantylamido)titanium dimethyl;
2,2-diphenylethylene(tetramethylcyclopentadienyl)-(4-tricyclo[2.2.1.02,6]heptylamido)titanium dimethyl;
The above named specific compounds wherein each Q is methyl are prepared from the corresponding compound wherein each Q is chloro. Thus, specific compounds within Formula V are those wherein each Q is chloro. Also, the corresponding compounds wherein each Q is phenyl, and M is zirconium or hafnium in place of titanium and (CR3R4)y is methylphenylmethylene, tetramethylethylene, tetraethylethylene, propylene, hexamethylpropylene, 1,1-dimethyl propylene, 1,1,2,2-tetramethylpropylene and the like, are also specific compounds within the above Formula V.
The compounds of the present invention can be made using the following general procedure and the specific examples set forth herein.
A lithiated monocyclopentadienyl compound (C5H5xe2x88x92xRx)Li is reacted with a dihalide of a bridging compound, R1R2TX2 wherein X is a halide radical, in a suitable solvent such as tetrahydrofuran. The resulting compound is represented by the formula (C5H5xe2x88x92xRx)TR1R2X.
The compound (C5H5xe2x88x92xRx)TR1R2X is then reacted with a lithiated amido compound of the formula LiHNxe2x80x94Rxe2x80x2 in a suitable solvent followed by addition of two equivalants of methyl lithium or similar compound, and subsequent addition of a Group IV metal compound complex such as MX4.2Et2O wherein M is a metal and X is a halide. The resulting compound is represented by the formula R1R2T(C5H4xe2x88x92xRx)(Nxe2x80x94Rxe2x80x2)MX2.
The compound R1R2T(C5H4xe2x88x92xRx)(Nxe2x80x94Rxe2x80x2)MX2 can be utilized as is or it can be converted to the corresponding dihydride, dialkyl, diaryl dicycloalkyl, dialkylaryl, dicycloalkylaryl, dialkylcycloalkyl, or mixtures thereof and the like to utilize with an activator which is not suitable for use when the Q ligands are halide and the like as more fully set forth below.
Monocyclopentadienyl metal compounds of the present invention have been discovered to produce a highly productive catalyst system which produces an ethylene-xcex1-olefin copolymer of significantly greater molecular weight and xcex1-olefin comonomer content as compared with other species of monocyclopentadienyl metal compounds when utilized in an otherwise identical catalyst system under identical polymerization conditions.
All of the above-defined monocyclopentadienyl metal compounds are useful, in combination with an activator or co-catalyst, to polymerize xcex1-olefins or other unsaturated hydrocarbon based monomers including cyclic olefins. Suitable activators include alumoxanes and activators comprising a cation and a non-coordinating compatible anion.
The alumoxane component is an oligomeric compound which may be represented by the general formula (R10xe2x80x94Alxe2x80x94O)m which is a cyclic compound, or may be R11(R12Alxe2x80x94Oxe2x80x94)mAlR132 which is a linear compound. An alumoxane is generally a mixture of both the linear and cyclic compounds. In the general alumoxane formula R10, R11, R12 and R13 are, independently a C1-C5 alkyl radical, for example, methyl, ethyl, propyl, butyl or pentyl and xe2x80x9cmxe2x80x9d is an integer from 1 to about 50. Most preferably, R10, R11, R12 and R13 are each methyl and xe2x80x9cmxe2x80x9d is at least 4. When an alkyl aluminum halide is employed in the preparation of the alumoxane, one or more R10-13 groups may be halide.
As is now well known, alumoxanes can be prepared by various procedures. For example, a trialkyl aluminum may be reacted with water, in the form of a moist inert organic solvent; or the trialkyl aluminum may be contacted with a hydrated salt, such as hydrated copper sulfate suspended in an inert organic solvent, to yield an alumoxane. Generally, however prepared, the reaction of a trialkyl aluminum with a limited amount of water yields a mixture of both linear and cyclic species of alumoxane.
Suitable alumoxanes utilized in the catalyst systems of this invention are those prepared by the hydrolysis of a trialkylaluminum; such as trimethylaluminum, triethylaluminum, tripropylaluminum; triisobutylaluminum, dimethylaluminumchloride, diisobutylaluminumchloride, diethylaluminumchloride, and the like. The most preferred alumoxane for use is methylalumoxane (MAO). Methylalumoxanes having an average degree of oligomerization of from about 4 to about 25 (xe2x80x9cmxe2x80x9d=4 to 25), with a range of 13 to 25, are the most preferred.
Modified alumoxanes can also be utilized. Examples of such modified alumoxanes are those disclosed in U.S. Pat. No. 5,041,584; EP 0 516 476; and EP 0 561 476 which are incorporated herein by reference.
Activators comprising a non-coordinating compatible anion component are described in U.S. Pat. No. 5,198,401 which is incorporated herein by reference. Compounds useful as the activator compound, in the preparation of the catalyst comprise a cation, preferably a Bronsted acid capable of donating a proton, and a compatible non-coordinating anion containing a single coordination complex comprising a charge-bearing metal or metalloid core which is relatively large (bulky), capable of stabilizing the active catalyst species (the Group IV-B cation) which is formed when the metallocene and activator compounds are combined, and said anion is sufficiently labile to be displaced by olefinic, diolefinic and acetylenically unsaturated substrates or other neutral Lewis bases such as ethers, nitrites and the like. It is well known that reactive cations other than Bronsted acids capable of donating a proton are also useful. Examples of such other cations include ferrocenium triphenylcarbonium and triethylsilylinium cations. Any metal or metalloid capable of forming a coordination complex which is resistant to degradation by water (or other Bronsted or Lewis Acids) may be used or contained in the anion of the second activator compound. Suitable metals include, but are not limited to, aluminum, gold, platinum and the like. Suitable metalloids include, but are not limited to, boron, phosphorus, silicon and the like.
Compounds containing anions which comprise coordination complexes containing a single metal or metalloid atom are, of course, well known and many, particularly compounds containing a single boron atom in the anion portion, are available commercially. See, for example, U.S. Pat. No. 5,278,119. In light of this, salts containing anions comprising a coordination complex containing a single boron atom are preferred. In general, the second activator compounds useful in the preparation of the catalysts of this invention may be represented by the following general formula:
[(Lxe2x80x2xe2x80x94H)+]d[(Mxe2x80x2)m+Qxe2x80x3xe2x80x21Qxe2x80x3xe2x80x22 . . . Qxe2x80x3xe2x80x2n]dxe2x88x92
wherein:
Lxe2x80x2 is a neutral Lewis base;
H is a hydrogen atom;
[Lxe2x80x2-H] is a Bronsted acid;
Mxe2x80x2 is a metal or metalloid;
Qxe2x80x3xe2x80x21 to Qxe2x80x3xe2x80x2n are, independently, hydride radicals, bridged or unbridged dialkylamido radicals, alkoxide and aryloxide radicals, hydrocarbyl and substituted hydrocarbyl radicals, halocarbyl and substituted halocarbyl radicals, and hydrocarbyl- and halocarbyl-substituted organometalloid radicals and any one, but not more than one, of Q1 to Qn may be a halide radical;
m is an integer representing the formal valence charge of Mxe2x80x2;
n is the total number of ligands Q; and
d is an integer representing the total charge on the anion.
Activator compounds comprising boron which are particularly useful in the preparation of catalysts of this invention are represented by the following general formula:
[Lxe2x80x2xe2x80x94H]+[BAr1Ar2X3X4]
wherein:
Lxe2x80x2 is a neutral Lewis base;
H is a hydrogen atom;
[Lxe2x80x2xe2x80x94H]+is a Bronsted acid;
B is boron in a valence state of 3+;
Ar1 and Ar2 are the same or different substituted-aromatic hydrocarbon radicals and may be linked to each other through a stable bridging group; and
X3 and X4 are, independently, hydride radicals, halide radicals, with the proviso that only X3 or X4 will be halide, hydrocarbyl radicals, substituted-hydrocarbyl radicals, halocarbyl radicals, substituted-halocarbyl radicals, hydrocarbyl- and halocarbyl-substituted organometalloid radicals, dialkylamido radicals, and alkoxy and aryloxy radicals.
In general, Ar1 and Ar2 may, independently, be any aromatic or substituted-aromatic hydrocarbon radical. Suitable aromatic radicals include, but are not limited to, phenyl, naphthyl and anthracenyl radicals. Suitable substituents on useful substituted-aromatic hydrocarbon radicals, include, but are not necessarily limited to, hydrocarbyl radicals, organometalloid radicals, alkoxy radicals, alkylamido radicals, fluoro and fluorohydrocarbyl radicals and the like such as those useful as X3 or X4. The substituent may be ortho, meta or para, relative to the carbon atom bonded to the boron atom. When either or both X3 and X4 are a hydrocarbyl radical, each may be the same or a different aromatic or substituted-aromatic radical as are Ar1 and Ar2, or the same may be a straight or branched alkyl, alkenyl or alkynyl radical, a cyclic hydrocarbon radical or an alkyl-substituted cyclic hydrocarbon radical. X3 and X4 may also, independently, be alkoxy or dialkylamido radicals, hydrocarbyl radicals and organometalloid radicals and the like. As indicated supra, Ar1 and Ar2 may be linked to each other. Similarly, either or both of Ar1 and Ar2 could be linked to either X3 or X4. Finally, X3 and X4 may also be linked to each other through a suitable bridging group.
Illustrative, but not limiting, examples of boron compounds which may be used as an activator component in the preparation of the improved catalysts of this invention are trialkyl-substituted ammonium salts such as triethylammonium tetra(phenyl)boron, tripropylammonium tetra(phenyl)boron, tri(n-butyl)ammonium tetra(phenyl)boron, trimethylammonium tetra(p-tolyl)boron, trimethylammonium tetra(octolyl)boron, tributylammonium tetra(pentafluorophenyl)boron, tripropylammonium tetra(o,p-dimethylphenyl)boron, tributylammonium tetra(m,m-dimethylphenyl)boron, tributylammonium tetra(p-trifluoromethylphenyl)boron, tributylammonium tetra(pentafluorophenyl)boron, tri(n-butyl)ammonium tetra(o-tolyl)boron and the like; N,N-dialkyl anilinium salts such as N,N-dimethylanilinium tetra(phenyl)boron, N,N-diethylanilinium tetra(phenyl)boron, N,N-2,4,6-pentamethylanilinium tetra(phenyl)boron and the like; dialkyl ammonium salts such as di(isopropyl)ammonium tetra(pentafluorophenyl)boron, dicyclohexylammonium tetra(phenyl)boron, and the like; and triaryl phosphonium salts such as triphenylphosphonium tetra(phenyl)boron, tri(methylphenyl)phosphonium tetra(phenyl)boron, tri(dimethylphenyl)phosphonium tetra(phenyl)boron and the like.
Similar lists of suitable compounds containing other metals and metalloids which are useful as activator components could be made, but such lists are not deemed necessary to a complete disclosure. In this regard, it should be noted that the foregoing list is not intended to be exhaustive and other boron compounds that would be useful as well as useful compounds containing other metals or metalloids would be readily apparent, from the foregoing general equations, to those skilled in the art.
Also useful are neutral Lewis acid ioning activators. An example of such activator is trisperfluorinated phenyl boron (B[pfp]3).
It is important to continued polymerization operations that either the metal cation initially formed from the metallocene, or a decomposition product thereof, be a relatively stable catalyst. It is also important that the anion of the activator compound be chemically stable and bulky. Further, when the cation of the activator component is a Bronsted acid, it is important that the acidity of the activator compound be sufficient, relative to the metallocene, to facilitate the needed proton transfer. Conversely, the basicity of the metal complex must also be sufficient to facilitate the needed proton transfer. In general, metallocenes in which the Q ligands can be hydrolyzed by aqueous solutions can be considered suitable metallocenes for forming the catalysts described herein, because water (our reference Bronsted acid) is a weaker acid than the ammonium ions used as cation in our preferred ion-exchange reagents. This concept allows one of ordinary skill in the art to choose useful metallocene components because stability to water is a basic chemical property easily determined experimentally or by using the chemical literature.
In view of the above, when utilizing an activator comprising a non-coordinating compatible anion, the metal component should be one wherein each Q is selected from the group consisting of hydride and substituted and unsubstituted hydrocarbyl radicals. Preferred Q ligands are hydride, C1-C12 alkyl and C6-C12 alkaryl and silyl radicals. Most preferred are those Q ligands selected from methyl and benzyl radicals. The preferred metal component species for use with an activator comprising a noncoordinating compatible anion are those set forth above wherein each Q is methyl. Such compounds can be generated in situ by combining a metal component wherein Q is other than a hydride or hydrocarbyl radical with an agent, e.g., any alkylating agent, and optionally, the activator component (e.g., an alumoxane or alkyl aluminum).
In one embodiment of the invention, the chemical reactions which occur upon combination of a monocyclopentadienyl metal compound with a non-coordinating compatible anion activator compound may be represented by reference to the general formulae set forth herein as follows: 
or 
wherein v is an inteager 0xe2x89xa6vxe2x89xa6w
Bxe2x80x2 represents the anion portion of a compatible activator corresponding to the general formulae set forth in Equation I. When the monocyclopentadienyl metal compound and the non-coordinating compatible anion activator components used to prepare the improved catalysts of the present invention are combined in a suitable solvent or diluent, all or a part of the cation of the activator (the acidic proton) combines with one of the substituents on the metallocene compound. In the case where the metallocene component has a formula corresponding to that of the general formula above, a neutral compound is liberated, which neutral compound either remains in solution or is liberated as a gas. In this regard, it should be noted that if either Q in the metallocene component is a hydride, hydrogen gas may be liberated. Similarly, if either Q is a methyl radical, methane may be liberated as a gas. In the cases where the first component wherein two Q form an alkylidene or cyclometalled hydrocarbyl diradical has a formula corresponding to those of general formulae of the reaction sequence shown directly above, the substituent on the metal is protonated but no substituent is liberated. In general, the rate of formation of the products in the foregoing reaction equations will vary depending upon the choice of the solvent, the acidity of the [Lxe2x80x2xe2x80x94H]+ selected, the particular Lxe2x80x2, the anion, the temperature at which the reaction is completed and the particular monocyclopentadienyl derivative of the metal selected.
As indicated, the improved catalyst compositions of the present invention will, preferably, be prepared in a suitable solvent or diluent. Suitable solvents or diluents include any of the solvents known in the prior art to be useful as solvents in the polymerization of olefins, diolefins and acetylenically unsaturated monomers. Suitable solvents, then, include, but are not necessarily limited to, straight and branched-chain hydrocarbons such as isobutane, butane, pentane, hexane, heptane, octane and the like; cyclic and alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane and the like and, particularly aromatic and alkyl-substituted aromatic compounds such as benzene, toluene, xylene and the like. Suitable solvents also include liquid olefins which may act as monomers or comonomers including ethylene, propylene, butadiene, cyclopentene, hexene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1,4-hexadiene, 1-octene, 1-decene and the like. Suitable solvents further include basic solvents which are not generally useful as polymerization solvents when conventional Ziegler-Natta type polymerization catalysts are used such as chlorobenzene.
Catalysts of this invention which are highly productive may be prepared at ratios of monocyclopentadienyl metal compound to non-coordinating compatible anion activator of 10:1 to about 1:1, preferably about 3:1 to 1:1.
With respect to the combination of a monocyclopentadienyl metal compound and non-coordinating compatible anion activator compound to form a catalyst of this invention, it should be noted that the two compounds combined for preparation of the active catalyst must be selected so as to avoid transfer of a fragment of the activator compound anion, particularly an aryl group, to the monocyclopentadienyl metal cation, thereby forming a catalytically inactive species. When anions consisting of hydrocarbyl anions are used, there are several means of preventing anion degradation and formation of inactive species. One method is to carry out the protonolysis process in the presence of small Lewis bases such as tetrahydrofuran. Discrete complexes can be isolated from these reactions, but the Lewis base is insufficiently labile to be displaced readily by olefin monomers, resulting in, at best, catalysts of very low activity. Another method of avoiding deleterious anion degradation is by steric hindrance. Anions of the second component which contain aryl groups can be made more resistant to degradation by introducing substituents in the ortho positions of the phenyl rings. While active metallocene polymerization catalysts can be generated by this method, the complex reaction chemistry often prevents characterization of the catalytically active species. Steric hindrance can also result from substitutions on the cyclopentadienyl rings of the monocyclopentadienyl metal compound component. Hence, wherein the mono(cyclopentadienyl) metal compound used is a [peralkyl-substituted monocyclopentadienyl] Group IVB metal compound, the high degree of substitution on the cyclopentadienyl ring creates sufficient bulkiness that the Lewis base generated by the protonolysis reaction may not coordinate to the metal. Also polyarylborate anions without substituents on the aryl rings may not transfer aryl fragments to generate catalytically inactive species.
Another means of rendering the anion of the activator compound more resistant to degradation is afforded by fluoride substitution, especially perfluoro substitution, in the anion thereof. One class of suitable non-coordinating anions can be represented by the formula [B(C6F5)3Qxe2x80x3xe2x80x2] where Qxe2x80x3xe2x80x2 is a monoanionic non-bridging radical as described above. The preferred anion of the activator compound of this invention, tetra(pentafluorophenyl)boron, hereafter referred to for convenience by the notation [B(C6F5)4], or [B(pfp)4], is virtually impervious to degradation and can be used with a much wider range of monocyclopentadienyl metal cations, including those without substitution on the cyclopentadienyl rings, than anions comprising hydrocarbyl radicals.
Since this anion has little or no ability to coordinate to the monocyclopentadienyl metal cation and is not degraded by the monocyclopentadienyl metal cation, structures of the ion-pair catalysts using the [B(pfp)4] anion depend on steric hindrance of substituents on the cyclopentadienyl ring of the substituent on the nitrogen of the amido ligand monocyclopentadienyl metal compound, the nature of the cation of the activator component, the Lewis base liberated from the protonolysis reaction, and the ratio at which the monocyclopentadienyl metal and activator component are combined. Thus, preferred catalyst systems having a non-coordinating compatible ion activator are those compounds of the above Formulas IV-VI, and, specifically, those species set forth above, in combination with [B(pfp)4]. If Lewis bases other than that liberated from the proton transfer process are present, they may complex to the metal to form modified catalysts of this invention.
Catalyst Systems
The catalyst systems employed in the method of the invention comprise a complex formed upon admixture of the metal component with an activator component. The catalyst system may be prepared by addition of the requisite metal component and either one or more alumoxane components or one or more non-coordinating anion components, or a combination of both, to an inert solvent in which olefin polymerization can be carried out by a solution, slurry or bulk phase polymerization procedure. Additional co-catalysts and/or scavenger compounds, e.g., alkyl aluminum or alkyl boron compounds, may also be included.
The catalyst system may be conveniently prepared by placing the selected metal component and the selected activator component, in any order of addition, in an alkane or aromatic hydrocarbon solventxe2x80x94preferably one which is also suitable for service as a polymerization diluent. Where the hydrocarbon solvent utilized is also suitable for use as a polymerization diluent, the catalyst system may be prepared in situ in the polymerization reactor. Alternatively, the catalyst system may be separately prepared, in concentrated form, and added to the polymerization diluent in a reactor. Or, if desired, the components of the catalyst system may be prepared as separate solutions and added to the polymerization diluent in a reactor, in appropriate ratios, as is suitable for a continuous liquid phase polymerization reaction procedure. Alkane and aromatic hydrocarbons suitable as solvents for formation of the catalyst system and also as a polymerization diluent are exemplified by, but are not necessarily limited to, straight and branched chain hydrocarbons such as isobutane, butane, pentane, hexane, heptane, octane and the like, cyclic and alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane and the like, and aromatic and alkyl-substituted aromatic compounds such as benzene, toluene, xylene and the like. Suitable solvents also include liquid olefins which may act as monomers or comonomers including ethylene, propylene, 1-butene, 1-hexene and the like.
In accordance with this invention, when the activator is alumoxane, optimum results are generally obtained wherein the Group IV B metal compound is present in the polymerization diluent in a concentration of from about 0.0001 to about 1.0 millimoles/liter of diluent and the alumoxane component is present in an amount to provide a molar aluminum to transition metal ratio of from about 1:1 to about 20,000:1. Where the activator is one comprising a non-coordinating compatible anion and a cation, such activator is present in an amount sufficient to provide a molar ratio of metal component of from 10:1 to about 1:10. Sufficient solvent should be employed so as to provide adequate heat transfer away from the catalyst components during reaction and to permit good mixing.
The catalyst system ingredientsxe2x80x94that is, the Group IV B metal component, the activator, and polymerization diluentxe2x80x94can be added to the reaction vessel rapidly or slowly. The temperature maintained during the contact of the catalyst components can vary widely, such as, for example, from xe2x88x92100xc2x0 to 300xc2x0 C. Greater or lesser temperatures can also be employed. Preferably, during formation of the catalyst system, the reaction is maintained within a temperature of from about 25xc2x0 to 100xc2x0 C., most preferably about 25xc2x0 C.
Polymerization Process
A typical polymerization process of the invention comprises the steps of contacting ethylene and a C3-C20 olefin alone, or with other unsaturated monomers including C3-C20 olefins, C4-C20 diolefins, and/or acetylenically unsaturated monomers with a catalyst comprising, in a suitable polymerization diluent, a monocyclopentadienyl metal compound, as described above, and an activator. The olefin monomers include xcex1-olefins as well as cyclic olefins such as, for example, cyclohexene, norborene, alkyl-substituted norborenes and the like. For example, a catalyst comprising a monocyclopentadienyl metal compound as described above and either 1) a non-coordinating compatible anion activator or 2) an alumoxane activator. The alumoxane activator is utilized in an amount to provide a molar aluminum to titanium metal ratio of from about 1:1 to about 20,000:1 or more. The non-coordinating compatible anion activator is utilized in an amount to provide a molar ratio of monocyclopentadienyl metal compound to non-coordinating anion of 10:1 to about 1:10. The above reaction is conducted by reacting such monomers in the presence of such catalyst system at a temperature of from about xe2x88x92100xc2x0 C. to about 300xc2x0 C. preferably 20xc2x0 C. to 250xc2x0 C., most preferably from 50xc2x0 C. to 200xc2x0 C. for a time of from about 1 second to about 10 hours to produce a copolymer having a weight average molecular weight of from about 1,000 or less to about 5,000,000, preferably 1,000 to 1.5 million, and a molecular weight distribution of from about 1.5 to about 15.0, preferably less than 5 and most preferably less than 4.
In a preferred embodiment of the process of this invention the catalyst system is utilized in the liquid phase (slurry, solution, suspension or bulk phase or combination thereof, high pressure fluid phase or gas phase polymerization of an olefin monomer. When utilized in a gas phase, slurry phase or suspension phase polymerization, the catalyst systems will preferably be supported catalyst systems. See also, for example, U.S. Pat. No. 5,057,475, WO 94/03506, which is incorporated herein by reference. Such catalyst systems can also be utilized in a gas phase process without a support as described in U.S. Pat. No. 5,317,036. Such catalyst systems can also include other well known additives such as, for example, scavengers. See, for example, U.S. Pat. No. 5,153,157 and WO 94/07927 (Apr. 14, 1994) which are incorporated herein by reference. These processes may be employed singularly or in series. The liquid phase process comprises the steps of contacting an ethylene and an olefin monomer with the catalyst system in a suitable polymerization diluent and reacting the monomers in the presence of the catalyst system for a time and at a temperature sufficient to produce an ethylene-xcex1-olefin copolymer of high molecular weight.
The monomers for such process comprise ethylene in combination with an xcex1-olefin having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms, most preferably 3 to 8 carbon atoms, for the production of an ethylene-xcex1-olefin copolymer. It should be appreciated that the advantages as observed in an ethylene-xcex1-olefin copolymer produced with a catalyst system of this invention would also be expected to be obtained in a copolymer of different xcex1-olefins wherein ethylene is not used as a monomer as viewed in comparison to a copolymer of the same or different xcex1-olefins produced under similar polymerization conditions with a catalyst system which does not use a monocyclopentadienyl Group IV B metal compound as defined herein. Accordingly, although this invention is described with reference to an ethylene-xcex1-olefin copolymer and the advantages of the defined catalyst system for the production thereof, this invention is not to be understood to be limited to the production of an ethylene-xcex1-olefin copolymer, but instead the catalyst system hereof is to be understood to be advantageous in the same respects to the production of a copolymer composed of two or more C3 or higher xcex1-olefin monomers. Copolymers of higher xcex1-olefin such as propylene, butene, styrene or higher xcex1-olefins, cyclic olefins and diolefins can also be prepared. Conditions most preferred for the homo- or copolymerization of ethylene are those wherein ethylene is submitted to the reaction zone at pressures of from about 0.019 psia to about 50,000 psia and the reaction temperature is maintained at from about xe2x88x92100xc2x0 C. to about 300xc2x0 C. Where the activator is an alumoxane, the aluminum to transition metal molar ratio is preferably from about 1:1 to 20,000 to 1. A more preferable range would be 1:1 to 2000:1. The reaction time is preferably from about 10 seconds to about 4 hours.
Without limiting in any way the scope of the invention, one means for carrying out the process of the present invention for production of a copolymer is as follows: in a stirred-tank reactor liquid xcex1-olefin monomer is introduced, such as 1-butene. The catalyst system is introduced via nozzles in either the vapor or liquid phase. Feed ethylene gas is introduced either into the vapor phase of the reactor, or sparged into the liquid phase as is well known in the art. The reactor contains a liquid phase composed substantially of liquid xcex1-olefin comonomer, together with dissolved ethylene gas, and a vapor phase containing vapors of all monomers. The reactor temperature and pressure may be controlled via reflux of vaporizing xcex1-olefin monomer (autorefrigeration), as well as by cooling coils, jackets, etc. The polymerization rate is controlled by the concentration of catalyst. The ethylene content of the polymer product is determined by the ratio of ethylene to xcex1-olefin comonomer in the reactor, which is controlled by manipulating the relative feed rates of these components to the reactor.